US3519603A - Curable mixtures of diepoxy compounds,disecondary amines,and polyamines containing at least 3 active hydrogen atoms linked to nitrogen - Google Patents

Curable mixtures of diepoxy compounds,disecondary amines,and polyamines containing at least 3 active hydrogen atoms linked to nitrogen Download PDF

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US3519603A
US3519603A US732560A US3519603DA US3519603A US 3519603 A US3519603 A US 3519603A US 732560 A US732560 A US 732560A US 3519603D A US3519603D A US 3519603DA US 3519603 A US3519603 A US 3519603A
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nitrogen
epoxy resin
diamine
amine
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Friedrich Lohse
Rolf Schmid
Hans Batzer
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BASF Schweiz AG
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Ciba AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33365—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group
    • C08G65/33368—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group acyclic
    • C08G65/33372—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group acyclic acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • a curable epoxy resin mixture suitable for use as casting, impregnating or laminating resin, as binder, coating or sealing composition characterized in that it contains (I) a diepoxy compound containing two 1,2-epoxyethyl residues, (II) a di-secondary diamine of the formula HNA--NH 19 Claims in an amount of 0.3 to 0.9, preferably 0.5 to 0.8, equivalent of active hydrogen atoms linked with nitrogen for every equivalent of epoxide groups of the diepoxy compound (I), and in this formula R and R each represents an unsubstituted or alkylated saturated carbocycle or a ring system containing at least cyclic carbon atoms, and A represents an unsubstituted or alkylated polymethylene residue which may be interrupted by ether oxygen atoms and which contains in the linear chain directly connecting the two secondary nitrogen atoms at least 4 and preferably at least 6 carbon atoms, and (III) a polyamine
  • epoxy resins can be cured with aliphatic or cycloaliphatic polyamines.
  • resin+curing agent systems are in general distinguished by a relatively low curing temperature which is decisive for many applications and the cured resin+curing agent mixtures display quite good mechanical strength.
  • epoxy resin+amine curing agent systems it is also possible to manufacture cured, shaped structures having a high flexibility. 'However, it has not been possible in the past to combine the high strength values with a high stretchability, that is to say to obtain tough, shaped structures that combine a high tensile strength wih a high elongation at rupture.
  • the' processing properties are often extensively impaired by the relatively high viscosity of the epoxy resin+amine curing agent mixture and the resulting short pot life.
  • the present invention is based on the observation that flexibilized epoxy resin mixtures are obtained, which at worst involve the disadvantages of the hitherto known resin systems based on epoxy resins and polyamines only to a minor degree, by using as curing agent in specific proportions combinations of polyamines containing at least 3 amine-hydrogen atoms with certain mixed aliphatic-cycloaliphatic disecondary diamines, in which the two secondary nitrogen atoms are separated from each other by a polymethylene chain of at least 4 carbon atoms and in which, furthermore, the two secondary nitrogen atoms are substituted by a cycloaliphatic ring containing at least 5 cyclic carbon atoms.
  • the new epoxy resin+curing agent systems can as a rule be fully cured at a temperature of C. or below and have, compared with the known systems, a relatively low viscosity and especially a surprisingly long pot life (relatively slow rise in viscosity as a function of the time).
  • the resulting shaped structures are distinguished by surprisingly high strength values and high elongation at rupture.
  • the present invention provides curable epoxy resin mixtures suitable for use as casting, impregnating and laminating resins, as binders, coating compositions and sealing compositions, characterized in that they contain (I) a diepoxy compound containing two 1,2- epoxyethyl residues, (II) a disecondary diamine of the formula in an amount of 0.3 to 0.9, preferably 0.5 to 0.8, equivalent of active hydrogen atoms bound to nitrogen for every equivalent of epoxide groups of the diepoxy compound '(I) and in this formula R and R each represents an unsubstituted or alkylated saturated carbocycle or a cyclic system containing at least 5 cyclic carbon atoms, and A represents an unsubstituted or alkylated polymethylene residue which maybe interrupted by ether oxygen atoms, which contains in the linear chain directly linking the two secondary nitrogen atoms at least 4 and preferably at least 6 carbon atoms, and (III) a polyamine containing at least 3 active hydrogen atom
  • epoxyethyl residues CHz-CH- are, for example, butadiene diepoxide and divinylbenzene diepoxide.
  • diepoxy compounds (I) are preferred which contain two glycidyl groups.
  • basic polyepoxy compounds obtained by reacting primary aromatic monoamines such as aniline or toluidine, or secondary aromatic diamines such as 4,4'-di-(mono-methylamino)-di phenylmethane, with epichlorohydrin in presence of alkali; furthermore diglycidyl compounds obtained by reacting epichlorohydrin with heterocyclic nitrogen bases such as hydantoin, 5,5-dimethylhydantoin, parabanic 'acid, ethyleneurea, for example -N,N'-diglycidyl-5,S-dimethylhydantoin. It is also advantageous to use diglycidyl ethers or diglycidyl esters.
  • Preferred diglycidyl esters are those obtained by reacting a dicarboxylic acid with epichlorohydrin or dichlorohydrin in presence of an alkali.
  • diesters may be derived from aliphatic dicarboxylic acids such as succinic, adipic or sebacic acid, from aromatic dicarboxylic acids such as phthalic, isophthalic or terephthalic acid, or especially from hydroaromatic dicarboxylic acids such as tetrahydrophthalic, hexahydrophthalic or 4-methylhexahydrophthalic acid.
  • digylcidyl adipate diglycidyl phthalate, diglycidyl terephthalate, diglycidyl tetrahydrophthalate and digilycidyl hexahydrophthalate.
  • Preferred diglycidyl ethers are those obtained by etherifying a dihydric alcohol or diphenol with epichlorohydrin or dichlorohydrin in presence of alkali. These compounds may be "derived from glycols such as ethyleneglycol, diethyleneglycol, triethyleneglycol, 1,3-propyleneglycol, 1,4- butanediol, 1,5-pentanediol, -1,6-hexanediol, nitrogenous dialcohols, such as N-phenyldiethanolamine and especially from diphenols such as resorcinol, pyrocatechol, hy-
  • G is the residue of polybutyleneglycol with diepoxy compounds of the following constitution HOG -OH CH3 l R1(SCHzOIIz); OA ⁇ ;; O -NH@ NHOOX R in which n is an integer of at least 2, preferably 2 or 3; of average molecular Weight 980, from which the ter- X represents an oxygen or a sulphur atom; R stands for minal hydroxyl groups have been removed).
  • CH3- NHCOOG4OCONH CH3 a monovalent aliphatic residue which may be interrupted (where G; is the residue of polypropyleneglycol by oxygen or sulphur atoms or carboxylic acid ester groups; R represents an aliphatic residue containing a terminal 1,2-epoxyethyl group, which may be substituted by halogen atoms or interrupted by oxygen or sulphur of average molecular weight 440, from which the terminal hydroxyl groups have been removed);
  • A represents the residue of a glycol, poly- 7 glycol, thiodiglycol or poly(thiodiglycol) from which the terminal hydroxyl groups have been removed;
  • mr l or 2 HO G .()H and 2:1 or 2, preferably 1, or mixtures of such diepoxy compounds with the aforementioned diglycidyl compounds.
  • Diglycidyl compounds very suitable for the purposes of this invention are also the adducts, still containing terminal glycidyl groups, of a stoichiometric excess of conventional diglycidyl compounds, such as bisphenol A-diglycidyl ethers, hexaand tetrahydophthalic acid diglycidyl esters and an acid aliphatic polyester containing terminal carboxyl groups.
  • conventional diglycidyl compounds such as bisphenol A-diglycidyl ethers, hexaand tetrahydophthalic acid diglycidyl esters and an acid aliphatic polyester containing terminal carboxyl groups.
  • Suitable polyesters are, for example, condensates of adipic or sebacic acid with 1,4-butanediol, 1,6-hexanediol or neopentylglycol, which contain terminal carboxyl groups. These adducts are obtained by reacting such acid polyesters with a diglycidyl compound, the latter being used in excess. By curing mixtures of this invention containing such adducts as diepoxy compound shaped structures having considerable toughness are obtained.
  • the disecondary diamines of the Formula 1 used as curing agent component (II) in the resin+curing agent mixtures of this invention are most readily accessible by reacting 1 mol of a diprimary diamine of the formula (3) H N-ANH with a ketone of the formula to form the Schitfs 'base of the formula which is then hydrogenated to furnish the disecondary diamine of the Formula 1.
  • A has the same meaning as in Formula 1 and Z, together with the carbon atom linked by a double bond with oxygen or nitrogen respectively, forms a saturated or olefinically unsaturated carbocyclic ring or ring system containing at least 5 cyclic carbon atoms, which may be substituted by alkyl side-chains.
  • Diprimary amines of the Formula 3 suitable for the synthesis of the disecondary diamines of the Formula 1 are, for example, tetramethylenediamine, pentamethylenediamine and especially those which contain more than 6 carbon atoms in the carbon chain which links the primary amino groups, such as 1,12-diaminododecane and especially hexamethylenediamine and commercial trimethylhexamethylenediamine (isomer mixture of 2,2,4- trimethyl-hexamethylenediamine and 2,4,4-trimethylhexamethylenediamine).
  • disecondary diamines of the Formula 1 there may be mentioned N,N'-di (cyclopentyl) hexamethylenediamine,
  • curing agent component (II) in the resin-l-curing agent mixtures of this invention also disecondary diamines obtained by reacting cycloaliphatic amines with glycols under hydrogenating conditions according to the following scheme:
  • A represents a residue of a polyalkyleneglycol left on elimination of the terminal hydroxyl groups and R represents an unsubstituted, saturated carbocycle or ring system containing at least 5 endo-cyclic carbon atoms.
  • tributyleneglycol and higher polymers especially polypropyleneglycols and polybutyleneglycols.
  • cycloaliphatic amines which react with the glycols under hydrogenating conditions there may be used, for example, the following:
  • the polyamines containing at least 3 amino-hydrogen atoms, suitable for use as curing agent component (H1) in the curable resin-l-curing agent mixtures of this invention belong preferably to the aliphatic or cycloaliphatic series, though also those of the aromatic or araliphatic series may be used.
  • polyamines that contain 3 or more secondary amino groups and no primary amino groups, though diprimary or primary-secondary polyamines are preferred.
  • Suitable aromatic and araliphatic polyamines are, for example,
  • diprimary alkylenepolyamines such, for example, as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,2-propylenediamine, 1,3-propylenediamine, N-hydroxyalkyl-alkylenepolyamines such, for example, as
  • N-hydroxyethyl-ethylenediamine N-hydroxyethyl-pentamethylenediamine, N-hydroxypropyl-tetrarnethylenediarnine, N-hydroxyethyl-diethylenetriamine,
  • N,N"-dihydroxyethyl -diethylenetriamine N-hydroxypropyl-diethylenetriamine, N,N"-di- (hydroxypropyl -diethylenetriamine, N-hydroxyethyl-propylenediamine, N-hydroxypropyl-propylenediamine, N-hydroxyethyl-dipropylenetriamine.
  • Preferred use is made of long-chain polyamines of the aliphatic series such as tetramethylenediamine, pentamethylenediamine,
  • 1,12-diaminododecane and especially hexamethylenediamine and commercial trimethyl-hexamethylenediamine (isomer mixture of 2,2,4- trimethyl hexamethylenediamine and 2,4,4-trimethylenediamine). Furthermore, it is advantageous to use polyamines of the cycloaliphatic and aliphatic-cycloaliphatic series such as 1,2-diaminocyclohexane, 1,4-diaminocyclohexane,
  • the curable mixtures of this invention are cured to form shaped structures in known manner either at room temperature or with heating, as a rule within the temperature range from 50 to 100 C.
  • curing as used in this context describes the conversion of the above-mentioned diepoxides into insoluble and infusible cross-linked products, as a rule with simultaneous shaping to furnish shaped structures such as castings, mouldings or laminates or flat two-dimensional structures such as lacquer films or adhesive bonds.
  • the curable mixtures of this invention may be admixed at any stage prior to curing with other conventional additives such as fillers, dyestuffs, pigments, flame-proofing agents, mould release agents and the like; suitable extenders and fillers are, for example, glass fibres, carbon fibres, boron fibres, mica, quartz meal, cellulose, burnt kaolin, ground dolomite, colloidal silica having a large specific surface (Aerosil) or metal powders such as aluminium powder.
  • suitable extenders and fillers are, for example, glass fibres, carbon fibres, boron fibres, mica, quartz meal, cellulose, burnt kaolin, ground dolomite, colloidal silica having a large specific surface (Aerosil) or metal powders such as aluminium powder.
  • the importance of the fiexibilized curable mixtures of this invention resides both in the electrotechnical sphere, for example as casting or impregnating resins, potting and encapsulating compositions, for example for potting electronic components, and in the mechanical sector, for example as laminating resins or liners for vessels and tubes manufactured by winding glass fibres, as adhesives and binders for metal, wood and synthetic materials or as coating or pointing materials for the building industry.
  • curable epoxy resin mixtures may further be used with advantage in all technical spheres where conventional curable epoxy resin mixtures are employed, for example also as solvent-free paints, lacquers, dipping resins or moulding compositions.
  • N,N'-DI- (CYCLOPENTYL)-HEXAMETHYLENE- DIAMINE 580 grams (5 mols) of hexamethylenediamine are mixed with 500 ml. of ethanol and 924 g. (10 mols+2% excess) of cyclopentanone are added, whereupon a weakly exothermic reaction sets in. 30 grams of palladium carbon Pd) are added to the reaction mixture which is then hydrogenated at 60 C. under a hydrogen pressure of 60 atmospheres (gauge). After 6 hours the absorption of hydrogen ceases, whereupon the catalyst is filtered off and the reaction mixture concentrated and distilled, to yield at 119 C. under 0.03 mm. Hg pressure 908 g. of pure product, corresponding to a yield of 72% of the theoretical.
  • N,N'-DI-(CYCLOHEXYL)-2,4,4-(2,2,4)-TRI- METHYL-HEXAMETHYLENEDIAMINE 735 grams (4.68 mols) of commercial trimethyl-hexamethylenediamine (isomer mixture of 2,4,4-trim ethylhexamethylenediamine and 2,2,4-trimethyl-hexamethylenediamine) are cautiously mixed with 1100 g. (9.38
  • reaction mixture is mixed with 60 g. of palladium carbon 10% Pd) and fully hydrogenated at 60 C. under a hydrogen pressure of 60 atmospheres (gauge). The hydrogenation is completed after 11 hours. The batch is then filtered, concentrated and the crude product used as it is for curing operations described below.
  • Example 3 154 grams of hexahydrophthalic acid diglycidyl ester (I), containing 6.5 epoxide equivalents per kg., were mixed with 80.5 g. of N,N-di-(cyclopentyl)-hexamethylenediamine (II) and 19 g. of commercial trimethylhexamethylenediamine (III) [corresponding to a ratio of 0.6 equivalent of amine-hydrogen atom of diamine (II) and 0.5 equivalent of amine-hydrogen atom of diamine (III) for every epoxide equiXalent of the epoxy compound (I) the mixture exacuated to remove the air bubbles (as described in Example 1) and then poured into the heated tensile body moulds. After curing for 16 hours at 100 C. the mouldings revealed the following properties:
  • Example 4 153 grams of adipic acid diglycidyl ester (I), containing 6.53 epoxide equivalents per kg., were mixed with 84 g. of N,N-di-(cyclohexyl)-hexamethylenediamine (II) and 21.3 g. of 3-(aminomethyl) 3,5,5 trimethylcyclohexylamine (III) and the mixture after evacuation to remove the air bubbles poured into the tensile body moulds as described in Example 1. After curing for 16 hours at 100 C. the mouldings revealed the following properties:
  • Viscosity of the resin-l-curing agent mixture at 50 C. (a) immediately after mixingl470 centipoises (b) 1 hour after mixing-14,400 centipoises.
  • Tensile strength according to VSM1.52 kg. mm. Elongation at rupture according to VSM-390% When 0.85 mol of tetrahydrophthalic acid diglycidyl ester instead of hexahydrophthalic acid diglycidyl ester was used, all other conditions being identical, mouldings were obtained which revealed the followed properties:
  • disecondary diamine is of decisive importance to the flexibility of the mouldings.
  • the resin- ⁇ curing agent mixture described above was also used for coating aluminium surfaces which after been cured in a similar manner revealed excellent adhesion.
  • Example 14 Tensile strength according to.VSM-1.11 kg. mm. Elongation at rupture according to VSM70%
  • Example 15 22.3 grams (:1 epoxide equivalent) of the diglycidyl compound of the constitution tensile body moulds described in Example 1. After 16 hours curing at 90 C. the mouldings revealed the following properties:
  • Example 16 109 grams of the epoxy resin A of Example 1 were heated for 3 hours at 140 C. with 109 g. of an acid polyester of sebacic acid and neopentylglycol, acid equivalent weight 1070 g. (obtained by heating 11 mols of sebacic acid with mols of neopentylglycol at 140 to 180 C.) to form an adduct containing 2.3 epoxide equivalents per kg. 218 g. of this adduct together with another 92.5 g. of epoxy resin A are heated to 90 C. and thoroughly mixed with 122 g.
  • Example 17 185 grams of the epoxy resin A of Example 1 were thoroughly mixed at 80 C. with 154.5 g. of N,N'-di- (cyclohexyl)-polypropyleneglycol diamine (prepared as described under 5 from polypropyleneglycol of average molecular weight 425 and cyclohexylamine under..hydro-.
  • a curable epoxy resin composition which comprises (I) a diepoxy compound containing two 1,2-epo-xyethyl residues, (II) a disecondary diamine of the formula HNANH 1'1. ,1. q in an amount of 0.3 to 0.9 equivalent of active hydrogen atoms linked with nitrogen for every equivalent of epoxide groups of the diepoxy compound (I), and in this formula R and R each represents a member selected from the group consisting of an unsubstituted saturated carbocyclic ring containing at least 5 and at most 6 endocyclic carbon atoms, and an alkyl substituted carbocyclic ring containing at least 5 and at most 6 endocyclic carbon atoms, and A represents a member selected from the group consisting of an unsubstituted polymethylene residue, an alkyl substituted polymethylene residue, an unsubstituted poly(oxypolymethylene) residue and an alkyl substituted poly(oxypolymethylene) residue which contain in the linear chain
  • R and R each represents a member selected from the group consisting of an unsubstituted saturated carbocyclic ring containing at least and at most 6 endocyclic carbon atoms and an alkyl substituted carbocyclic ring containing at least 5 and at most 6 endocyclic carbon atoms and A represents a polyglycol residue which is obtained by removal of the terminal hydroxyl groups and which contains in the linear chain directly connecting the two secondary nitrogen atoms at least 4 carbon atoms, and (III) a polyamine, which contains at least 3 active hydrogen atoms linked with nitrogen, in an amount of 0.2 to 0.8 equivalent of active hydrogen atoms linked with nitrogen for every epoxide equivalent of the diepoxy compound (I).
  • a curable epoxy resin composition according to claim 1, comprising (I) a diepoxy compound containing two 1,2-epoxyethy1 residues, (II) a disecondary diamine of the formula in an amount of 0.5 to 0.8 equivalent of active hydrogen atoms linked with nitrogen for every equivalent of epoxide groups of the diepoxy compound (I), and in this formula R and R each represents a member selected from the group consisting of an unsubstituted saturated carbocyclic ring containing at least 5 and at most 6 endocyclic carbon atoms and an alkyl substituted carbocyclic ring containing at least 5 and at most 6 endocyclic carbon atoms and A represents a polyglycol residue which is obtained by removal of the terminal hydroxyl groups and which contains in the linear chain directly connecting the two secondary nitrogen atoms at least 6 carbon atoms, and (III) a polyamine, which contains at least 3 active hydrogen atoms linked with nitrogen, in an amount of 0.4 to 0.6 equivalent of active hydrogen atoms linked
  • An epoxy resin composition according to claim 1 comprising as diepoxy compound (I) a diglycidyl compound.
  • An epoxy resin composition according to claim 1 comprising as diglycidyl compound the diglycidyl ether of a diphenyl.
  • An epoxy resin composition according to claim 1 comprising as diglycidyl compound the diglycidyl ester of a dicarboxylic acid.
  • An epoxy resin composition according to claim 1 comprising as diglycidyl compound an adduct of (a) a stoichiometric excess of a member selected from the group consisting of a diphenol diglycidyl ether and a dicarboxylic acid diglycidyl ester and (b) an acid aliphatic polyester containing two terminal carboxyl groups.
  • An epoxy resin composition according to claim 1 comprising as diepoxy compound (I) a compound of the formula in which n is an integer of at least 2 and at most 3, X represents a member selected from the group consisting of an oxygen and a sulphur atom, R is a member selected from the group consisting of an n-valent aliphatic hydrocarbon residue, an n-valent aliphatic hydrocarbon residue interrupted by oxygen atoms, an n-valent hydrocarbon residue interrupted by sulphur atoms and n-valent aliphatic hydrocarbon residue interrupted by carboxylic acid ester groups, A represents a member selected from the group consisting of the residue obtained by removing the terminal hydroxyl groups from a glycol, the residue obtained by removing the terminal hydroxyl groups from a polyglycol, the residue obtained by removing the terminal hydroxyl groups from a thiodiglycol and the residue obtained by removing the terminal hydroxyl groups from a poly(thio)diglycol, m represents an integer of at
  • An epoxy resin composition according to claim 1 comprising as disecondary diamine a diamine of the formula in which A represents a member selected from the group consisting of an unsubstituted hexamethylene residue and a methyl substituted hexamethylene residue and nis an integer of at least 4 and at most 5.
  • An epoxy resin composition according to claim 10 comprising as disecondary diamine N,N'-di-(cyclohexyl)- hexamethylenediamine.
  • An epoxy resin composition according to claim 10 comprising as disecondary diamine N,N'-di-(cyclopentyl -hexa-methylenediamine.
  • An epoxy resin composition according to claim 10 comprising as disecondary diamine a member selected from the group consisting of N,N-dicyclohexyl-2,4,4-trimethyl-hexamethylene-diamine and/or N,N'-dicyclohexyl-2,2,4-trimethylhexamethylenediamine.
  • An epoxy resin composition according to claim 10 comprising as disecondary diamine an N,N-di-(cyclohexyl)-polypropy1eneglyco1 diamine.
  • An epoxy resin composition according to claim 15 comprising as diprimary polyamine a cycloaliphatic diprimary polyamine.
  • An epoxy resin composition according to claim 15 comprising as cycloaliphatic diprimary polyamine 2,2-bis- (4-aminocyclohexyl)-propane.
  • An epoxy resin composition according to claim 15 comprising 3 (aminomethyl)-3,5,S-trimethyl-cyclohexylamine as cycloaliphatic diprimary polyamine.
  • An epoxy resin composition according to claim 15 comprising as diprimary polyamine hexamethylenediamine or commercial trimethylhexamethylene diamine 19 20 (isomer mixture of 2,4,4 -trimethy1- hexamethylenedia- WILLIAM H. SHORT, Primary Examiner mine and 2,2,4-trimethy1hexamethylenediamine).

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US732560A 1967-06-08 1968-05-28 Curable mixtures of diepoxy compounds,disecondary amines,and polyamines containing at least 3 active hydrogen atoms linked to nitrogen Expired - Lifetime US3519603A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH812867A CH481963A (de) 1967-06-08 1967-06-08 Neue härtbare Mischungen aus Diepoxydverbindungen, disekundären Aminen sowie mindestens 3 Aminwasserstoffatome enthaltenden Polyaminen
CH1121767A CH495947A (de) 1967-06-08 1967-08-09 Verfahren zur Herstellung von neuen disekundären Diaminen

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US748590A Expired - Lifetime US3609121A (en) 1967-06-08 1968-07-30 Curable epoxy resin compositions containing novel disecondary diamines

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AT (1) AT283755B (en:Method)
BE (2) BE716251A (en:Method)
CH (2) CH481963A (en:Method)
DE (1) DE1768888A1 (en:Method)
ES (1) ES354785A1 (en:Method)
FR (2) FR1567764A (en:Method)
GB (2) GB1197836A (en:Method)
NL (2) NL161176C (en:Method)

Cited By (9)

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US4108824A (en) * 1977-07-11 1978-08-22 Shell Oil Company Low-temperature curable saturated epoxy resin compositions
US4195152A (en) * 1977-08-01 1980-03-25 Henkel Corporation N-Alkyl polyamines and curing of epoxy resins therewith
US5464924A (en) * 1994-01-07 1995-11-07 The Dow Chemical Company Flexible poly(amino ethers) for barrier packaging
US5908598A (en) * 1995-08-14 1999-06-01 Minnesota Mining And Manufacturing Company Fibrous webs having enhanced electret properties
US20070073030A1 (en) * 2005-03-28 2007-03-29 Albemarle Corporation Chain Extenders
US20070270566A1 (en) * 2005-03-28 2007-11-22 Albemarle Corporation Chain Extenders
US20080033210A1 (en) * 2005-03-28 2008-02-07 Albemarle Corporation Diimines and secondary diamines
US20100160592A1 (en) * 2007-01-10 2010-06-24 Albemarle Corporation Formulations For Reaction Injection Molding And For Spray Systems
US20230014155A1 (en) * 2019-12-17 2023-01-19 Dentsply Sirona Inc. Dental root canal filling composition

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US4181682A (en) * 1978-01-09 1980-01-01 Texaco Development Corp. Aminated propoxylated polybutanediols
US4255468A (en) * 1979-10-12 1981-03-10 H. B. Fuller Company Method of marking paved surfaces and curable two-part epoxy systems therefor
US4423170A (en) * 1982-10-15 1983-12-27 Texaco Inc. One component water reduced epoxy adhesives
US4946924A (en) * 1987-12-21 1990-08-07 Texaco Chemical Company Secondary isopropyl amine derivatives of polyoxyalkylene diamines and triamines
US4886867A (en) * 1988-11-14 1989-12-12 Texaco Chemical Company Novel compositions from polyoxyalkylene amines and epoxides
GB8918965D0 (en) * 1989-08-19 1989-10-04 Bp Chem Int Ltd Chemical process
JP2974382B2 (ja) * 1990-08-10 1999-11-10 住友ゴム工業株式会社 軟質エポキシ樹脂組成物
WO1992007893A1 (en) * 1990-11-06 1992-05-14 Anchor Continental, Inc. Epoxy-based elastomer
ATE195544T1 (de) * 1993-12-21 2000-09-15 Ciba Sc Holding Ag Zusammensetzungen auf der basis von epoxidharzen, zähigkeitsvermittlern und aminen
DE19512316A1 (de) * 1995-04-01 1996-10-02 Hoechst Ag Härtungsmittel für elastische Epoxidharz-Systeme
WO2002028849A1 (en) * 2000-10-04 2002-04-11 Henkel Loctite Corporation Reworkable epoxidized 1-(cyclo)alkenyl ether/polycarboxylic acid product
BRPI0620897A2 (pt) * 2005-12-30 2011-11-29 Albemarle Corp misturas de diaminas com cor reduzida
WO2008112636A1 (en) * 2007-03-13 2008-09-18 Albemarle Corporation Chain extenders
BRPI0721666A2 (pt) * 2007-06-15 2014-03-18 Dow Global Technologies Inc Processo para preparação de um compósito moldado reforçado
MX2011006417A (es) * 2010-06-24 2012-01-02 Momentive Specialty Chem Inc Sistemas de epoxi mejorados para materiales compuestos.
EP3255080B1 (de) * 2016-06-10 2018-08-15 Evonik Degussa GmbH Epoxidharz-zusammensetzung enthaltend 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propan-1,3-diamin (am-cpda) als härter

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US2817644A (en) * 1955-12-30 1957-12-24 Shell Dev Process for curing polyepoxides and resulting products

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US2817644A (en) * 1955-12-30 1957-12-24 Shell Dev Process for curing polyepoxides and resulting products

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108824A (en) * 1977-07-11 1978-08-22 Shell Oil Company Low-temperature curable saturated epoxy resin compositions
US4195152A (en) * 1977-08-01 1980-03-25 Henkel Corporation N-Alkyl polyamines and curing of epoxy resins therewith
US5464924A (en) * 1994-01-07 1995-11-07 The Dow Chemical Company Flexible poly(amino ethers) for barrier packaging
US5908598A (en) * 1995-08-14 1999-06-01 Minnesota Mining And Manufacturing Company Fibrous webs having enhanced electret properties
US5919847A (en) * 1995-08-14 1999-07-06 Minnesota Mining And Manufacturing Company Composition useful for making electret fibers
US5968635A (en) * 1995-08-14 1999-10-19 Minnesota Mining And Manufacturing Company Fibrous webs useful for making electret filter media
US5976208A (en) * 1995-08-14 1999-11-02 Minnesota Mining And Manufacturing Company Electret filter media containing filtration enhancing additives
US6002017A (en) * 1995-08-14 1999-12-14 Minnesota Mining And Manufacturing Company Compounds useful as resin additives
US6268495B1 (en) 1995-08-14 2001-07-31 3M Innovative Properties Company Compounds useful as resin additives
US20070270566A1 (en) * 2005-03-28 2007-11-22 Albemarle Corporation Chain Extenders
US20070073030A1 (en) * 2005-03-28 2007-03-29 Albemarle Corporation Chain Extenders
US20080033210A1 (en) * 2005-03-28 2008-02-07 Albemarle Corporation Diimines and secondary diamines
US20080194788A1 (en) * 2005-03-28 2008-08-14 Albemarle Corporation Diimines and Secondary Diamines
US7767858B2 (en) 2005-03-28 2010-08-03 Albemarle Corporation Diimines and secondary diamines
US20110137005A1 (en) * 2005-03-28 2011-06-09 Albemarle Corporation Chain Extenders
US7964695B2 (en) 2005-03-28 2011-06-21 Albemarle Corporation Chain extenders
US8076518B2 (en) 2005-03-28 2011-12-13 Albemarle Corporation Chain extenders
US8080626B2 (en) 2005-03-28 2011-12-20 Albemarle Corporation Chain extenders
US8212078B2 (en) 2005-03-28 2012-07-03 Albemarle Corporation Diimines and secondary diamines
US20100160592A1 (en) * 2007-01-10 2010-06-24 Albemarle Corporation Formulations For Reaction Injection Molding And For Spray Systems
US8143365B2 (en) 2007-01-10 2012-03-27 Albemarle Corporation Formulations for reaction injection molding and for spray systems
US20230014155A1 (en) * 2019-12-17 2023-01-19 Dentsply Sirona Inc. Dental root canal filling composition

Also Published As

Publication number Publication date
DE1768888A1 (de) 1972-02-17
ES354785A1 (es) 1969-11-01
NL161176B (nl) 1979-08-15
NL6808056A (en:Method) 1968-12-09
DE1770539B2 (de) 1976-09-30
BE719225A (en:Method) 1969-02-10
BE716251A (en:Method) 1968-12-09
US3609121A (en) 1971-09-28
NL161176C (nl) 1980-01-15
DE1770539A1 (de) 1971-10-28
FR1567764A (en:Method) 1969-05-16
CH481963A (de) 1969-11-30
AT283755B (de) 1970-08-25
CH495947A (de) 1970-09-15
GB1197836A (en) 1970-07-08
FR1575141A (en:Method) 1969-07-18
NL6811301A (en:Method) 1969-02-11
GB1219024A (en) 1971-01-13

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